Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Japanese Patent Application
No. Hei. 1-342,384
POLYOXYMETHYLENE COMPOSITION
CField of Industrial Application?
The present invention relates to a polyoxymethylene
composition having an improved releasability from a
mold~and giving out only a faint smell of formaldehyde
in the course of the molding.
CPrior Art
A polyoxymethylene resin is produced by
polymerizing formaldehyde or trioxane which is a
cyclic oligomer of formaldehyde or by copolymerizing
trioxane with a comonomer such as a cyclic ether or
cyclic formal. The terminals thereof are stabilized
and an antioxidant and other thermal stabilizers are
added thereto to prevent the degradation thereof.
Sterically hindered phenol compounds and
sterically hindered amine compounds are proposed as
the antioxidants to be added to the polyoxymethylene
~~~a~~1
resin and other thermal stabilizers proposed heretofore
include polyamides, urea derivatives, amidine
compounds, alkali metal hydroxides, alkaline earth
metal hydroxides, and organic and inorganic acid
salts. However, the polyoxymethylene resin composition
containing such compounds has defects which are
exhibited in the molding step as follows: owing to
the effects of heat and oxygen, it is apt to give
out a smell of formaldehyde in a cylinder of a molding
machine to pollute the working (hygienic) environment
and when molding is conducted over a long time, a
fine powder or tarry substance (MD) is deposited on
the inner surface of the mold to impair the appearance
of the obtained molding. Although various ideas
and proposals were heretofore made, satisfactory
results could not always be obtained.
( Summary of the invention )
After intensive investigations of stabilizers,
the inventors have found that the intended object
can be attained by incorporating a specified amine
polymer along with an antioxidant. The present
invention has been completed on the basis of this
finding.
Thus the present invention relates to a
polyoxymethylene composition containing 0.01 to 5~
CA 02033041 2000-06-27
73372-56
3
by weight, based on the polyoxymethylene, of a hindered phenol
antioxidant and 0.01 to 5% by weight of an amine polymer having
a molecular weight of at least 1000 and comprising structural
units of the following formula (1):
H R
I I
C-C (1)
H X
i
NH2
wherein R represents a hydrogen atom, an alkyl group, a
N
phenyl group, an alkyl-substituted phenyl group or X~ , and X
represents an alkylene group, a carbonyl group, a
carboxyalkylene group, an alkyleneoxycarbonylalkyl group, a
phenylene group, an alkyl-substituted phenylene group, an amido
group or an alkyleneamido group, or X may optionally be absent.
A detailed description will now be made on the
constituents of the composition of the present invention.
The amine polymer used in the present invention is
any of those comprising the structural units of the above
formula (1) and having a molecular weight of at least 1000.
Preferred are homopolymers,
4
;~'~;~;~ a~34~,
crosslinked polymers or copolymers having a molecular
weight of at least 1000 and comprising allylamine,
acrylamide, acrylic hydrazide, methacrylic hydrazide,
an aminoalkyl acrylate, an aminoalkyl methacrylate
or a vinylalkylamine, or a copolymer thereof with
ethylene, propylene, butylene, butadiene, styrene,
acrylonitrile, an acrylic ester or a methacrylic
ester. These amine polymers may be used either
singly or in combination of two or more or them.
The molecular weight of the amine polymer used
is at least 1000, preferably at least 5000 and still
preferably 10000 to 100000. When the molecular weight
is less than 1000, the polymer oozes out of the
composition or the molding produced therefrom, so
that an intended effect of the present application
cannot be obtained.
Among these amine polymers, preferred are
homopolymers, crosslinked polymers and copolymers
comprising allylamine or acrylamide as the structural
units and having a molecular weight or at least 1000.
When the amine polymer is used incombination
with the hindered phenol antioxidant, it exhibits
effects of inhibiting the decomposition of the
polyoxymethylene and capturing formaldehyde formed
by the decomposition. Therefore the formation of
~~s~~~~~,
the decomposition gas is considerably inhibited.
It is also supposed that deposits are scarcely
formed in the mold, since the amine polymer per se
is scarcely sublimed or decomposed.
The hindered phenol antioxidants used in the
present invention include 2,2'-methylenebis(4-methyl-
6-t-butylphenol), 1,6-hexanediol bisC3-(3,5-di-t-
butyl-4-hydroxyphenyl)propionateJ, pentaerythritol
tetrakisC3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate7,
triethylene glycol bisC3-,(3-t-butyl-5-methyl-4-
hydroxyphenyl)propionate~, 1,3,5-trimethyl-2,4,6-
tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, n-
octadecyl 3-(4'-hydroxy-3',5'-di-t-butylphenyl)-
propionate, 4,4'-methylenebis(2,6-di-t-butylphenol),
4,4'-butylidenebis(6-t-butyl-3-methylphenol), 2,2'-
thiodiethylbisC3-(3,5-di-t-butyl-4-hydroxyphenyl)-
propionate7, di-stearyl 3,5-di-t-butyl-4-hydroxybenzyl-
phosphonate, 2-t-butyl-6-(3-t-butyl-S-methyl-2-
hydroxybenzyl)-4-methylphenyl acrylate and N,N'-
hexamethylenebis(3,5-di-t-butyl-4-hydroxy-
hydrocinnamamide). They may be used either singly
or in combination of two or more of them. Among
them, particularly preferred are 1,6-hexanediolbisC3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionate7,
pentaerythritol tetrakisC3-(3,5-di-t-butyl-4-
"
.,
hydroxyphenyl)propionate7, triethylene glycolbisC3-
(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate7 and
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-
hydrocinnamide).
The amount of the hindered phenol antioxidant
used in the present invention is 0.01 to S~ by weight,
preferably 0.1 to 3~ by weight, based on the poly-
oxymethylene, and the amount of the amine polymer
is 0.01 to 5~ by weight, preferably 0.01 to l~s by
weight. When these amounts are insufficient, no
sufficient effects can be obtained, while when they
are excess, the heat stabilizing effect reaches
saturation and rather discoloration is caused
unfavorably.
The polyoxymethylenes into which the above-
described additives axe to be incorporated are
polymeric compounds comprising oxymethylene groups
(-CH20-) as the main constitutive units. They may
be any of polyoxymethylene homopolymers, and
copolymers, terpolymers and block copolymers
comprising the oxymethylene groups and a small amount
of other constitutive units. The molecule of the
polyoxymethylene may be not. only linear but also
branched or crosslinked. The degree of polymerization
thereof is not particularly limited.
d
The composition of the present invention may
contain, if necessary, one or more compounds selected
from among a nitrogenous compound other than the amine
polymer of the present application, an alkali or
alkaline earth metal hydroxide, an inorganic acid
salt, and a metallic compound such as a carboxylate
or alkoxide.
The nitrogenous compounds herein include
polyamides such as homopolymeric and copolymeric
polyamides, e.g. nylon 12, nylon 6-10 a.nd nylon
6~66~610, substituted polyamides having a methylol
group or the like, nylon salts, polyesteramides
synthesized from a combination of caprolactone and
caprolactam; as well as polyaminotriazoles, heat
condensation products synthesized from dicarboxylic
dihydrazide and urea by heating, nitrogen-containing
polycondensates synthesized from urea and a diamine,
heat condensation product of urea synthesized by
heating urea, uracils, cyanoguanidines, dicyandiamide,
guanamine (2,4-diamino-sym-triazine), melamine
(2,4,6-triamino-sym-traizine), N-butylmelamine, N-
phenylmelamine, N,N-diphenylmelamine, N,N-diallyl-
melamine, N,N',N " -triphenylmelamine, N,N',N'-
trimethylolmelamine, benzoguanamine (2,4-diamino-
6-phenyl-sym-triazine), 2,4-diamino-6-methyl-sym-
U
triazine, 2,4-diamino-6-butyl-sym-triazine, Z,4-
diamino-6-benzyloxv-sym-triazine, 2,4-diamino-6-
butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-
triazine, 2,4-diamino-6-chloro-sym-triazine, ?,4-
diamino-6-mercapto-sym-triazine, 2,4-dihydroxy-6-
amino-sym-triazine (ammelide), 2-hydroxy-4,6-diamino-
sym-triazine (ammeline) arid N,N,N',N'-tetracyano-
ethylbenzoguanamine.
The metallic compounds include hydroxides of
sodium, potassium, magnesium, calcium and barium,
carbonates, phosphates, silicates, borates, oxalates,
malonates, succinates, adipates, and salts of higher
(C1~ to Ca2) fatty acids such as stearic acid and
substituted higher fatty acids having a substituent
such as a hydroxyl group. They further include basic
compounds having at least one tertiary nitrogen atom
and a metal carboxylate group in one molecule such
as sodium N-methyliminodiacetate, trisodium
nitrilotriacetate, tetrasodium ethylenediamine-
tetraacetate, tetrapotassium ethylenediaminetetra-
acetate, dicalcium ethylenediaminetetraacetate,
pentasodium diethylenetriaminepentaacetate,
pentapo'tassium diethylenetriaminepentaacetate,
hexasodium triethylenetetraminehexaacetate and
tetrasodium ethylenedioxybis(ethylamine)-N,N,N',N'-
9
tetraacetate.
The composition of the present invention may
contain one or more of known additives such as
lubricant, nucleating agent, releasing agent,
antistatic agent, surfactant, organic polymeric
material, and inorganic or organic, fibrous, powdery
or platy filler in order to impart desired properties
thereto depending on the use thereof.
The process for producing the composition of
the present invention is not particularly limited.
It can be easily produced with a known apparatus
and by a known process for the production of ordinary
resin compositions-. For example, it can be produced
by (i) a process wherein the components are mixed
together, the mixture is kneaded and extruded with
an extruder to form pellets and the pellets are
shaped into a molding, (ii) a process wherein two
or more kinds of pellets having different compositions
from each other are produced, and. predetermined
amounts of the pellets are mixed together and subjected
to the molding to obtain a molding having an intended
composition or (iii) a process wherein one or more
components are directly placed in a molding machine.
It is also preferred that a part of the resin
components is finely pulverized and then mixed with
other components in order to obtain a homoceneous
mixture.
The resin composition of the present invention
can be produced by any of extrusion molding, injection
molding, compression molding, vacuum molding, blow
molding and foam molding processes.
CExamples~
The following Examples will further illustrate
the present invention, which by no means limit the
invention.
In the following Examples, the evaluation methods
were as follows:
1) Moldability
A sample of the polyoxymethylene composition
was continuously molded (for about 24 h) with an
injection molding machine under predetermined
conditions and the following tests were conducted:
(1) Formaldehyde smell in the molding step:
Twenty moldings (about 30 mm x about S mm
about 1.5 mm) immediately after the production
were placed in a zippered polyethylene bag
(size: 10 cm x 14 cm) and sealed. After a
predetermined period of time, the bag was
opened and a smell given out was classified
into four ranks:
11 ~~~a~3~4~.
A: no irritating smell,
B: only a faint smell of formaldehyde,
C: relatively strong smell of formaldehyde, and
D: strong smell of formaldehyde.
(2) Quantity of deposit in the mold:
The extent of staining of the mold azter
the continuous molding was classified into five
ranks:
A: no staining,
B : suite s light staining ,
C: a little staining,
D., relatively severe staining, and
E: severe staining.
2) Weight loss upon heating:
A weight loss caused when 5 g of the sample was
heated at 235°C in air for 45 min was determined.
Examples 1 to 7
A hindered phenol antioxidant and an amine
polymer listed in Table 1 were added to a polyoxy-
methylene copolymer (Duracon, a product of Polyplastics
Co., Ltd.) in a ratio as specified in 'fable 1, mixed
and extruded with an extruder to form a pelletized
composition. The pellets were subjected to the
above-described tests. The results are given in
Table 1.
°
~!~~,~~~~
Comparative Examples 1 to S
Pellets were produced in the same manner as that
of Examples 1 to 7 except that the amine compound
was replaced with 0.3~ by weight of a substance listed
in Tab le 1. The results are given in Table 1 together
with those of the Examples.
It will be apparent from the above description
and Examples that according to the present invention,
the thermal stability of the polyoxymethylene is
remarkably improved and a resin composition quite
preferred from the viewpoint of the working and
hygienic environment which stains the molds only
slightly even after the continuous molding over a
long period of time and which gives out a remarkably
weakened smell of formaldehyde in the molding process
can be obtained.
13
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